CN105732957B - Based on blue or green A A type conjugated polymers of isoindigo and preparation method and application - Google Patents

Based on blue or green A A type conjugated polymers of isoindigo and preparation method and application Download PDF

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CN105732957B
CN105732957B CN201610206416.8A CN201610206416A CN105732957B CN 105732957 B CN105732957 B CN 105732957B CN 201610206416 A CN201610206416 A CN 201610206416A CN 105732957 B CN105732957 B CN 105732957B
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octyldodecyl
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pinacoldiboronisoindigo
conjugated polymer
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CN105732957A (en
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黄辉
王小芬
吕磊
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University of Chinese Academy of Sciences
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Abstract

The present embodiments relate to a kind of A A type conjugated polymer blue or green based on isoindigo and preparation method and application, the general structure of the A A type conjugated polymer blue or green based on isoindigo is：The Ar is aromatic compound fragment, and R is C1 C32 alkyl, C2 C32 alkylene, C2 C32 alkynes base, ether epoxide, alkyl streptamine or sulfydryl；N is the integer more than or equal to 4 and less than or equal to 100.The A A type conjugated polymer blue or green based on isoindigo provided in an embodiment of the present invention, dissolubility is good, absorbance is strong, absorption region is wide, there is higher utilization rate to sunshine, lumo energy is low, fullerene and its derivative can be replaced to prepare all-polymer organic photodetector and organic solar batteries as acceptor material.

Description

Based on blue or green A-A type conjugated polymers of isoindigo and preparation method and application
Technical field
The present invention relates to a kind of conjugated polymer, more particularly to a kind of A-A type conjugated polymer blue or green based on isoindigo and its Preparation method and application.
Background technology
Conjugatd polymerses cause the extensive concern of scientist as a kind of new functional material in recent years.Mesh Before, organic electro-optic device has been realized in the partial function of inorganic semiconductor photoelectric device, such as organic electroluminescent LED, has Machine solar cell, organic field effect tube and there is machine information storage.
Conjugated polymer is also used as the active layer material of photo-detector, does mainly polymerizeing for active layer material at present Thing/fullerene.And based on the photo-detector of polymer/fullerene, Liang Yongye seminars by the optimization of molecular structure successfully Dark current is reduced to 2.6 × 10-10A·cm-2At-0.2V and its transmission performance and photoelectric properties are not had much affect.- Specific detecivity reaches 10 under 0.2V bias13Jones, and linear dynamic range is very wide, at monochromatic light (under 550nm green glow) Strength Changes are from nWcm-2To mWcm-2(Zhang,L.；Yang,T.；Shen,L.；Fang,Y.；Dang,L.；Zhou,N.； Guo,X.；Hong,Z.；Yang,Y.；Wu,H.；Huang,J.；Liang,Y.Advanced materials 2015,27, 6496)。
Although fullerene and its derivative have its unique advantage as acceptor material, its spherical structure first can make electricity Lotus realizes three-dimensional transmission, also there is high electron mobility in composite membrane；Secondly it has relatively low lowest unoccupied molecular orbital (LUMO) energy level fast and effeciently can obtain electronics from donor material, improve the separation of carrier.Therefore, current efficient device Mainly deploy around fullerene derivate.But fullerene acceptor material is there is also some shortcomings, for example they are visible In light absorptivity it is low, prepare and purification difficult, cost it is higher, be difficult to due to level structure the open-circuit voltage of adjusting means by Limitation etc., limits the further raising of organic solar batteries efficiency to a certain extent.Preferable acceptor material must pull against These defects, it is complementary to realize that Donor acceptor materials optical absorbs, at utmost using sunshine, and realize higher open circuit electricity Pressure, so as to obtain more preferable device performance, non-fullerene conjugated polymer acceptor material is easy to chemical modification, and cost is relatively low, It is easy to produce in enormous quantities；And their absworption peak is wider and energy level easy-regulating, convenience match with numerous donor materials, because This possible substituted fullerene and its derivative are widely studied as new acceptor material in organic photodetector.
It is currently based on the blue or green polymer of isoindigo highest energy transformation efficiency (PCE) is obtained in organic solar batteries and is 8.2% (Deng, Y.；Liu,J.；Wang,J.；Liu,L.；Li,W.；Tian,H.；Zhang,X.；Xie,Z.；Geng,Y.； Wang,F.Advanced materials 2014,26,471)；However, this kind of polymer, primarily as donor material, this is Because the carrier of its prevailing transmission is hole.For develop with electric transmission polymer can make isoindigo birds of the same feather flock together compound make For type n semiconductor material, it is further applied in all-polymer solar cell or photo-detector, is still urgently to be resolved hurrily Problem.
The content of the invention
It is an object of the invention to provide a kind of A-A type conjugated polymer blue or green based on isoindigo and preparation method and application, The A-A type conjugated polymer dissolubilities of the present invention are good, and absorbance is strong, and absorption region is wide, there is higher utilization rate to sunshine, can To pass through blue or green (isoindigo, acceptor material (the Acceptor)) unit of isoindigo and strong electron deficient molecule naphthalimide (NDI) Synthesized with imidodicarbonic diamide (PDI) (Acceptor) by Suzuki coupling reactions.Due to NDI, PDI has very strong electrophilic Group, thus can effectively reduce the lumo energy (close with fullerene and its derivative) of polymer.Therefore this analog copolymer Fullerene can be replaced to be applied to as acceptor material in organic solar batteries and photo-detector, and obtain preferable effect Fruit.
To achieve the above object, in a first aspect, the invention provides a kind of structure of the A-A types conjugated polymer to lead to Shown in formula such as formula (I)；
Formula (I)
The Ar is aromatic compound fragment, and R is C1-C32 alkyl, C2-C32 alkylene, C2-C32 alkynes Base, ether epoxide, alkyl streptamine or sulfydryl；N is the integer more than or equal to 4 and less than or equal to 100；
Wherein, the Ar is specially：
The chemical formula of the A-A types conjugated polymer is specifically as formula (II), formula (III) or formula (IV) are shown；
Formula (II)；
Formula (III)；
Formula (IV).
It is poly- in second aspect, the A-A types conjugation shown in the formula (II) provided the invention provides a kind of above-mentioned first aspect The method of compound, including；
Under the catalytic action of three (dibenzalacetone) two palladium and three (o-methyl-phenyl) phosphorus, 6,6 '-(N, N ' -2- Octyldodecyl)-Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6- Dibromonaphthalene-1,4,5,8-bis (dicarboximide) are reacted, and obtain being conjugated shown in the formula (II) Polymer；
Wherein, described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) mol ratio is 1：0.99-1.05；
The dosage of described three (dibenzalacetone) two palladium be 6,6 '-(N, N ' -2-octyldodecyl) - The 1-2% of Pinacoldiboronisoindigo mole dosages, the dosage of three (o-methyl-phenyl) phosphorus for 6,6 '-(N, N ' -2- Octyldodecyl) the 5%-6% of-Pinacoldiboronisoindigo mole dosages.
Preferably, described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N ' - Bis (2-octyldodecyl) -2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) mol ratio For 1：1.
Preferably, the temperature of the reaction is 90 DEG C -100 DEG C, and the reaction time is 70-72 hours.
It is further preferred that described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo with N, N '-bis (2-octyldodecyl) -2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) Reaction is carried out in organic solvent；
The organic solvent is：With the toluene of arbitrary proportion mixing and the mixture of water.
In the third aspect, the A-A shown in formula (III) or formula (IV) provided the invention provides a kind of above-mentioned first aspect The method of type conjugated polymer, including：
Under the catalytic action of tetrakis triphenylphosphine palladium, 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10- Perylene Diimide are reacted, and obtain conjugated polymer shown in formula described in claim 1 (III)；Or
Under the catalytic action of tetrakis triphenylphosphine palladium, 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-Bis (2-Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide is reacted, and obtains conjugated polymer shown in formula described in claim 1 (IV)；
Wherein, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Octyldodecyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05；
6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05；
The dosage of the tetrakis triphenylphosphine palladium be 6,6 '-(N, N ' -2-octyldodecyl) - The 4%-6% of Pinacoldiboronisoindigo mole dosages.
Preferably, described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N ' - Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：1；
Described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：1.
Preferably, the temperature of the reaction is 90 DEG C -100 DEG C, and the reaction time is 40-48 hours.
It is further preferred that the reaction is carried out in organic solvent；
The organic solvent is：With the toluene of arbitrary proportion mixing and the mixture of water.
In fourth aspect, the invention provides a kind of application of the A-A type conjugated polymers described in above-mentioned first aspect, institute A-A types conjugated polymer is stated to be used to prepare photovoltaic device as acceptor material.It is provided in an embodiment of the present invention blue or green based on isoindigo A-A type conjugated polymers, dissolubility is good, and absorbance is strong, and absorption region is wide, there is higher utilization rate to sunshine, has relatively low Lumo energy, can replace fullerene as acceptor material applied in organic solar batteries and photo-detector, and obtain Preferable effect.
Brief description of the drawings
Fig. 1 is conjugated polymer PIIG-NDI (OD) provided in an embodiment of the present invention, PIIG-PDI (EH) and PIIG-PDI (OD) uv-visible absorption spectra；
Fig. 2 is conjugated polymer provided in an embodiment of the present invention as the organic optical detection of all-polymer made of acceptor material The structural representation of device or solar cell；
Fig. 3 is the dark current and photocurrent curve that conjugated polymer provided in an embodiment of the present invention is used for photo-detector；
Fig. 4 is that conjugated polymer provided in an embodiment of the present invention is used for photo-detector when bias is -1V in different wave length Under spectral responsivity；
Fig. 5 is that conjugated polymer provided in an embodiment of the present invention is used for photo-detector when bias is -1V in different wave length Under external quantum efficiency (EQE)；
Fig. 6 is that conjugated polymer provided in an embodiment of the present invention is used for photo-detector when bias is -0.2V in different ripples Specific detecivity under long；
Fig. 7 is the J-V curves that conjugated polymer provided in an embodiment of the present invention is used for organic solar batteries.
Embodiment
Below by drawings and examples, technical scheme is described in further detail.Need what is illustrated It is that following embodiments are not limiting the scope of the invention, the improvement and change that any invention is made on the basis of the present invention Change all within protection scope of the present invention.
Embodiment one
A kind of A-A type conjugated polymer blue or green based on isoindigo is present embodiments provided, shown in general structure such as formula (I)；
Formula (I)
Wherein, R is C1-C32 alkyl, C2-C32 alkylene, C2-C32 alkynes base, ether epoxide, alkyl streptamine Or sulfydryl；N is the integer more than or equal to 4 and less than or equal to 100；
Ar is aromatic compound fragment, is specially：
Therefore, the chemical formula of the A-A type conjugated polymers of the present embodiment is specifically such as formula (II), formula (III) or formula (IV) institute Show；
Formula (II)；
Formula (III)；
Formula (IV).
The conjugated polymer of formula (II) is designated as PIIG-NDI (OD), and the conjugated polymer of formula (III) is designated as PIIG-PDI (OD), the conjugated polymer of formula (IV) is designated as PIIG-PDI (EH).Figure 1 illustrates PIIG-NDI (OD), PIIG-PDI (EH) and PIIG-PDI (OD) uv-visible absorption spectra.It was found from absorption spectrum, polymer has wide in visible region Absworption peak, this absorption to sunshine is highly beneficial, therefore available for the preparation of all-polymer photo-detector and solar cell.
Embodiment two
Present embodiments provide the method for preparing A-A type conjugated polymers PIIG-NDI (OD) shown in above-mentioned formula (II).
Under the catalytic action of three (dibenzalacetone) two palladium and three (o-methyl-phenyl) phosphorus, 6,6 '-(N, N ' -2- Octyldodecyl)-Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6- Reaction 70 is small at 90 DEG C -100 DEG C in organic solvent by dibromonaphthalene-1,4,5,8-bis (dicarboximide) When -72 hours, obtain above-mentioned formula (II) conjugated polymer.
In this method, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) mol ratio is 1：0.99-1.05, preferably 1：1.The dosage of three (dibenzalacetone) two palladium be 6,6 '-(N, N ' -2-octyldodecyl) - The 1%-2% of Pinacoldiboronisoindigo mole dosages, the dosage of three (o-methyl-phenyl) phosphorus for 6,6 '-(N, N '- 2-octyldodecyl) the 5%-6% of-Pinacoldiboronisoindigo mole dosages.Organic solvent is with arbitrary proportion The toluene of mixing and the mixture of water.
In the present embodiment, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo are under The method for stating document offer is synthesized：Kim,G.；Han,A.R.；Lee,H.R.；Lee,J.；Oh,J.H.；Yang, C.Chemical Communications 2014,50,2180；
N,N’-bis(2-octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) method provided according to following documents synthesizes：Kim,R.；Amegadze,P.S.K.；Kang,I.；Yun, H.-J.；Noh,Y.-Y.；Kwon,S.-K.；Kim,Y.-H.Advanced Functional Materials 2013,23, 5719；Vasimalla,S.；Senanayak,S.P.；Sharma,M.；Narayan,K.S.；Iyer,P.K.Chemistry of Materials 2014,26,4030.
Embodiment three
The present embodiment three provides A-A type conjugated polymer PIIG-NDI (OD) shown in a kind of specific above-mentioned formula (II) Method.
Illustrate first, it is compound 1 to be indicated in above-mentioned formula at 1, is compound 2 at sign 2.
Under nitrogen protection, into 25ml Schlenk pipes, 109.7mg (0.102mmol) compound 1 is added, 100.5mg (0.102mmol) compound 2,108.5mg (0.5mmol) potassium phosphate, 50mg tetrabutylammonium chloride, 1.4mg The Pd of (1.5mol%)2(dba)3, 1.9mg (6mol%) P- (o-Tol)3, 7ml toluene, 1.5ml water.In 90 DEG C of conditions Lower stirring reaction 3 days.
Then blocked again with phenyl boric acid pinacol fat and bromobenzene.
Obtain product PIIG-NDI (OD) 116.3mg, yield 69% from chloroform by soxhlet extraction afterwards.
Example IV
Present embodiments provide and prepare A-A type conjugated polymers PIIG-PDI (OD) shown in above-mentioned formula (III) and formula (IV) The method of shown A-A types conjugated polymer PIIG-PDI (EH).
Under the catalytic action of tetrakis triphenylphosphine palladium, 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10- Perylene Diimide are reacted -48 hours 40 hours at 90 DEG C -100 DEG C in organic solvent, are obtained shown in above-mentioned formula (III) Conjugated polymer.
Under the catalytic action of tetrakis triphenylphosphine palladium, 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-Bis (2-Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide is reacted -48 hours 40 hours at 90 DEG C -100 DEG C in organic solvent, obtains the conjugated polymers shown in above-mentioned formula (IV) Thing.
In this method, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2-Ethylhexyl) -1, 7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05；Preferably 1：1.Four (triphens Base phosphine) palladium dosage for 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo mole dosages 4%-6%.Organic solvent is the mixture with the toluene of arbitrary proportion mixing and water.
In the present embodiment, N, N '-Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide, N, N '-Bis (2-Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide are according to following The method synthesis that document provides：Mahmood,Z.；Xu,K.；B.；Cui,X.；Zhao,J.；Wang,Z.； Karatay,A.；Yaglioglu,H.G.；Hayvali,M.；Elmali,A.The Journal of Organic Chemistry 2015,80,3036.
Embodiment five
The present embodiment five provide A-A type conjugated polymer PIIG-PDI (OD) shown in a kind of specific above-mentioned (III) and A-A type conjugated polymers PIIG-PDI (EH) method shown in formula (IV).
Illustrate first, it is compound 1 to be indicated in above-mentioned formula at 1, is compound 3 at sign 3.
Polymer P IIG-PDI (OD) synthesis：Under nitrogen protection, into 25ml Schlenk pipes, 109.7mg is added The compound 1 of (0.102mmol), 110mg (0.102mmol) compound 3 (corresponding OD chains), 108.5mg (0.5mmol) phosphorus Sour potassium, 50mg tetrabutylammonium chloride, 1.4mg (1.5mol%) Pd2(dba)3, 1.9mg (6mol%) P- (o-Tol)3, 7ml toluene, 1.5ml water.Stirring reaction 2 days under the conditions of 90 DEG C.
Then blocked again with phenyl boric acid pinacol fat and bromobenzene.
Obtain product PIIG-PDI (OD) 107mg, yield 60% from chloroform by soxhlet extraction afterwards.
Polymer P IIG-PDI (EH) synthesis：Under nitrogen protection, into 25ml Schlenk pipes, 109.7mg is added The compound 1 of (0.102mmol), 78.8mg (0.102mmol) compound 3 (corresponding EH chains), 108.5mg's (0.5mmol) Potassium phosphate, 50mg tetrabutylammonium chloride, 1.4mg (1.5mol%) Pd2(dba)3, 1.9mg (6mol%) P- (o-Tol )3, 7ml toluene, 1.5ml water.Stirring reaction 2 days under the conditions of 90 DEG C.
Then blocked again with phenyl boric acid pinacol fat and bromobenzene.
Obtain product PIIG-PDI (EH) 90mg, yield 61% from chloroform by soxhlet extraction afterwards.
The A-A type copolymers that the above embodiment of the present invention is provided or prepared, acceptor material can be used as to be used to prepare photovoltaic Device, particularly prepare all-polymer organic photodetector and the organic solar electricity using present copolymer as acceptor material Pond.It is following that its preparation method and performance are illustrated by embodiment six.
Embodiment six
A-A types copolymer is used to prepare to the method for photovoltaic device in the present embodiment to be included：
Mixed using A-A types copolymer as acceptor material with identical donor material PTB7-Th, it is molten to add super dry chloroform Solution, it is equal to prepare a layer thickness by spin coating mode or other modes on the ITO electro-conductive glass through zinc peroxide modified One active layer film；In an instantiation, active layer thickness 120nm；Then by way of vacuum evaporation successively Molybdenum oxide and argent are prepared on active layer.Finally prepare reverse geometry device as shown in Figure 2.Device includes：Negative electrode (ito glass)/zinc oxide (electron transfer layer)/active layer (PTB7-Th:Copolymer)/molybdenum oxide (hole transmission layer)/anode (argent).
The performance for being used as all-polymer organic photodetector is as shown in table 1 below：
Table 1
Its performance test is as shown in Figure of description 3- Fig. 6.
Fig. 3 is the dark current and photocurrent curve that conjugated polymer is used for photo-detector；
Shown in Fig. 4 and Fig. 5, when be biased for -1V when, copolymer p IIG-PDI (EH) is polymerizeing entirely as acceptor material Spectral responsivity in object light detector shows maximum 0.13mVcm in 710nm-2, external quantum efficiency reaches at 630nm To 24%.From figure it can also be seen that, when PDI substitute NDI after, device performance is not only more stable, and performance be better than before Person.
It is -0.2V in bias shown in Fig. 6, the photo-detector for the all-polymer that the A-A copolymers based on different indigoid make Stable detectivity is shown in the range of 350~750nm, and peak reaches 6 × 1011Jones, this value is close to non-fowler Photo-detector of the alkene small molecule as acceptor material.
The performance of all-polymer organic solar batteries is as shown in table 2 below：
Fig. 7 is the J-V curves that conjugated polymer provided in an embodiment of the present invention is used for organic solar batteries.
The A-A type conjugated polymer dissolubilities of the present invention are good, and absorbance is strong, and absorption region is wide, has to sunshine higher Utilization rate, blue or green (isoindigo, acceptor material (the Acceptor)) unit of isoindigo and strong electron deficient molecule NDI and PDI can be passed through Synthesized by Suzuki coupling reactions.Due to NDI, PDI has very strong electron withdraw group, thus can effectively reduce polymer Lumo energy.Therefore this analog copolymer can be applied to organic solar batteries and optical detection instead of fullerene as acceptor material In device, and preferable effect is obtained.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include Within protection scope of the present invention.

Claims (11)

1. a kind of A-A type conjugated polymer blue or green based on isoindigo, it is characterised in that the structure of the A-A types conjugated polymer is led to Shown in formula such as formula (I)；
The Ar is aromatic compound fragment, and R is C1-C32 alkyl, C2-C32 alkylene, C2-C32 alkynes base, ether Epoxide, alkyl streptamine or sulfydryl；N is the integer more than or equal to 4 and less than or equal to 100；
Wherein, the Ar is specially：
。
2. the A-A type conjugated polymer blue or green based on isoindigo according to claim 1, it is characterised in that the A-A types conjugation The chemical formula of polymer is formula (II), formula (III) or formula (IV), and wherein formula (II) is：
Formula (III) is：
Formula (IV) is：
3. the method that one kind prepares the A-A type conjugated polymers shown in formula described in claim 2 (II), it is characterised in that described Method includes：
Under the catalytic action of three (dibenzalacetone) two palladium and three (o-methyl-phenyl) phosphorus, 6,6 '-(N, N ' -2- octyl groups ten Dialkyl group -) two boron isoindigo of-pinacol（6,6’-(N,N’-2-octyldodecyl)-Pinacoldiboronisoindigo）With N, N '-bis- (2- octyldodecyls) -2,6- dibromine naphthalenes -1,4,5,8- pairs (dicarboximides)（N,N’-bis(2- octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide)）Reacted, obtained Conjugated polymer shown in formula described in claim 2 (II)；
Wherein, described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo with
N,N’-bis(2-octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis (dicarboximide) mol ratio is 1：0.99-1.05；
The dosage of described three (dibenzalacetone) two palladium be 6,6 '-(N, N ' -2-octyldodecyl) - The 1-2% of Pinacoldiboronisoindigo mole dosages, the dosage of three (o-methyl-phenyl) phosphorus for 6,6 '-(N, N ' -2- Octyldodecyl) the 5%-6% of-Pinacoldiboronisoindigo mole dosages.
4. according to the method for claim 3, it is characterised in that described 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6-dibromonaphthalene-1,4, 5,8-bis (dicarboximide) mol ratio is 1：1.
5. according to the method for claim 3, it is characterised in that the temperature of the reaction is 90 DEG C -100 DEG C, the reaction time For 70-72 hours.
6. according to any described methods of claim 3-5, it is characterised in that described 6,6 '-(N, N ' -2- Octyldodecyl)-Pinacoldiboronisoindigo and N, N '-bis (2-octyldodecyl) -2,6- Dibromonaphthalene-1,4,5,8-bis (dicarboximide) reaction is carried out in organic solvent；
The organic solvent is：With the toluene of arbitrary proportion mixing and the mixture of water.
7. the method that one kind prepares formula described in claim 2 (III) or the A-A type conjugated polymers shown in formula (IV), its feature exist In methods described includes：
Under the catalytic action of tetrakis triphenylphosphine palladium, the boron isoindigo of 6,6 '-(N, N ' -2- octyldodecyls -)-pinacol two （6,6’-(N,N’-2-octyldodecyl)-Pinacoldiboronisoindigo）And N, N '-bis- (2- octyldodecyls Base) the bromo- 3,4,9,10- imidodicarbonic diamide of -1,7- two（N,N’-Bis(2-Octyldodecyl)-1,7-Dibromo-3,4,9, 10-Perylene Diimide）Reacted, obtain conjugated polymer shown in formula described in claim 2 (III)；Or
Under the catalytic action of tetrakis triphenylphosphine palladium, 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-bromo- 3,4,9,10- the imidodicarbonic diamide of bis- (2- ethylhexyls) -1,7- two（N, N’-Bis(2-Ethylhexyl)-1,7-Dibromo-3,4,9,10-Perylene Diimide）Reacted, obtain right It is required that conjugated polymer shown in 2 formulas (IV)；
Wherein, 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Octyldodecyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05；
6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：0.99-1.05；
The dosage of the tetrakis triphenylphosphine palladium be 6,6 '-(N, N ' -2-octyldodecyl) - The 4%-6% of Pinacoldiboronisoindigo mole dosages.
8. according to the method for claim 7, it is characterised in that described 6,6 '-(N, N ' -2-octyldodecyl) - Pinacoldiboronisoindigo and N, N '-Bis (2-Octyldodecyl) -1,7-Dibromo-3,4,9,10- Perylene Diimide mol ratio is 1：1；
Described 6,6 '-(N, N ' -2-octyldodecyl)-Pinacoldiboronisoindigo and N, N '-Bis (2- Ethylhexyl) -1,7-Dibromo-3,4,9,10-Perylene Diimide mol ratio is 1：1.
9. according to the method for claim 7, it is characterised in that the temperature of the reaction is 90 DEG C -100 DEG C, the reaction time For 40-48 hours.
10. according to any described methods of claim 7-9, it is characterised in that the reaction is carried out in organic solvent；
The organic solvent is：With the toluene of arbitrary proportion mixing and the mixture of water.
11. a kind of application of A-A type conjugated polymers as claimed in claim 1, it is characterised in that the A-A types conjugation is poly- Compound is used to prepare photovoltaic device as acceptor material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804271A (en) * 2012-11-06 2014-05-21 北京大学 Isoindigo compound containing electron-withdrawing groups, and preparation and application thereof
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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
n-Type Conjugated Polyisoindigos;Romain Stalder et. al.;《Macromolecules》;20110729;第44卷;6303-6310 *

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